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Issue 24, 2015
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The first example of a mixed valence ternary compound of silver with random distribution of Ag(I) and Ag(II) cations

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Abstract

The reaction between colourless AgSbF6 and sky-blue Ag(SbF6)2 (molar ratio 2 : 1) in gaseous HF at 323 K yields green Ag3(SbF6)4, a new mixed-valence ternary fluoride of silver. Unlike in all other Ag(I)/Ag(II) systems known to date, the Ag+ and Ag2+ cations are randomly distributed on a single 12b Wyckoff position at the [4 with combining macron] axis of the I[4 with combining macron]3d cell. Each silver forms four short (4 × 2.316(7) Å) and four long (4 × 2.764(6) Å) contacts with the neighbouring fluorine atoms. The valence bond sum analysis suggests that such coordination would correspond to a severely overbonded Ag(I) and strongly underbonded Ag(II). Thorough inspection of thermal ellipsoids of the fluorine atoms closest to Ag centres reveals their unusual shape, indicating that silver atoms must in fact have different local coordination spheres; this is not immediately apparent from the crystal structure due to static disorder of fluorine atoms. The Ag K-edge XANES analysis confirmed that the average oxidation state of silver is indeed close to +1⅓. The optical absorption spectra lack features typical of a metal thus pointing out to the semiconducting nature of Ag3(SbF6)4. Ag3(SbF6)4 is magnetically diluted and paramagnetic (μeff = 1.9 μB) down to 20 K with a very weak temperature independent paramagnetism. Below 20 K weak antiferromagnetism is observed (Θ = −4.1 K). Replacement of Ag(I) with potassium gives K(I)2Ag(II)(SbF6)4 which is isostructural to Ag(I)2Ag(II)(SbF6)4. Ag3(SbF6)4 is a genuine mixed-valence Ag(I)/Ag(II) compound, i.e. Robin and Day Class I system (localized valences), despite Ag(I) and Ag(II) adopting the same crystallographic position.

Graphical abstract: The first example of a mixed valence ternary compound of silver with random distribution of Ag(i) and Ag(ii) cations

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Publication details

The article was received on 19 Feb 2015, accepted on 18 Mar 2015 and first published on 27 Mar 2015


Article type: Paper
DOI: 10.1039/C5DT00740B
Citation: Dalton Trans., 2015,44, 10957-10968
  • Open access: Creative Commons BY license
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    The first example of a mixed valence ternary compound of silver with random distribution of Ag(I) and Ag(II) cations

    Z. Mazej, T. Michałowski, E. A. Goreshnik, Z. Jagličić, I. Arčon, J. Szydłowska and W. Grochala, Dalton Trans., 2015, 44, 10957
    DOI: 10.1039/C5DT00740B

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